Bisaminoalkoxysilane compounds and methods for using same to deposit silicon-containing films

ABSTRACT

Bisaminoalkoxysilanes of Formula I, and methods using same, are described herein:
 
R 1 Si(NR 2 R 3 )(NR 4 R 5 )OR 6   I
 
where R 1  is selected from hydrogen, a C 1  to C 10  linear alkyl group, a C 3  to C 10  branched alkyl group, a C 3  to C 10  cyclic alkyl group, a C 3  to C 10  alkenyl group, a C 3  to C 10  alkynyl group, a C 4  to C 10  aromatic hydrocarbon group; R 2 , R 3 , R 4 , and R 5  are each independently selected from hydrogen, a C 4  to C 10  branched alkyl group, a C 3  to C 10  cyclic alkyl group, a C 3  to C 10  alkenyl group, a C 3  to C 10  alkynyl group, and a C 4  to C 10  aromatic hydrocarbon group; R 6  is selected from a C 1  to C 10  linear alkyl group, a C 3  to C 10  branched alkyl group, a C 3  to C 10  cyclic alkyl group, a C 3  to C 10  alkenyl group, a C 2  to C 10  alkynyl group, and a C 4  to C 10  aromatic hydrocarbon group.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Divisional Application of U.S. application Ser.No. 15/017,913, filed Feb. 8, 2016, which claims the priority benefit ofU.S. Provisional Application No. 62/115,729, filed Feb. 13, 2015. Thedisclosure of these applications is hereby incorporated by reference intheir entirety.

BACKGROUND OF THE INVENTION

Described herein are volatile and thermally stable aminoalkoxysilanes,more specifically bisaminoalkoxysilanes, and methods for using same todeposit stoichiometric or non-stoichiometric silicon-containing filmssuch as, but not limited to, silicon oxide, silicon nitride, siliconoxynitride, silicon carboxide, and silicon oxycarbonitride films.

U.S. Pat. No. 4,491,669 discloses the preparation of pure mixedalkoxyaminosilanes corresponding to the general formula:R_(m)Si(OR′)_(n)(NR″R′″)_(p) wherein: R is hydrogen, short chain alkylor alkenyl or aryl; R″ and R′″ are separately either hydrogen, shortchain alkyl or aryl, at least one being other than hydrogen; R′ is shortchain alkyl or aryl; and m, n and p are integers such that m+n+p=4 and nand p are at least one each. The obtained compounds are employed inend-capping of polysiloxanes having terminal silane groups.

U.S. Pat. No. 4,345,088 discloses compounds having the formula(R)₂NXSiHOR where X is OR or N(R)₂ and wherein R is an alkyl of from oneto eight carbon atoms. These compounds are prepared by treatingtris(dialkylamino)hydridosilanes with alkanols.

U.S. Pat. No. 6,114,558 discloses the preparation ofalkyl(amino)dialkoxysilanes having the general formula RSi(NR¹R²)(OR³)₂,wherein R is a straight or branched chain alkyl of 1 to 20 carbon atoms,an arylalkyl or aryl radical, R¹ and R² are alkyl radicals of 1 to 6carbon atoms and one of them can be hydrogen, and R³ is an alkyl radicalof 1-6 carbon atoms with methyl being preferred. Thealkyl(amino)dialkoxysilanes are prepared by anhydrously reactingstoichiometric amounts of an alkoxysilane and an alkylaminomagnesiumchloride in a reverse addition process. The alkylamino magnesiumchloride is preferably prepared in situ by the reaction of a Grignardreagent (RMX) and an alkylamine in a suitable aprotic solvent, such astetrahydrofuran (THF). The reaction can be conducted in a temperaturerange of from 25°-75° C., without a catalyst, and the aprotic solvent isrecovered for re-use in the process. Thus, reaction ofisopropylmagnesium chloride with tert-butylamine in THF followed bytreatment with methyltrimethoxysilane gave 82%methyl(tert-butylamino)dimethoxysilane.

U.S. Pat. No. 7,524,735 discloses a method related to filling gaps onsubstrates with a solid dielectric material by forming a flowable filmin the gap. The flowable film provides a consistent, void-free gap fill.The film is then converted to a solid dielectric material. In thismanner gaps on the substrate are filled with a solid dielectricmaterial. According to various embodiments, the methods involve reactinga dielectric precursor with an oxidant to form the dielectric material.In certain embodiments, the dielectric precursor condenses andsubsequently reacts with the oxidant to form dielectric material. Incertain embodiments, vapor phase reactants react to form a condensedflowable film.

U.S. Pat. No. 7,943,531 discloses a method of depositing a silicon oxidelayer over a substrate in a deposition chamber. A firstsilicon-containing precursor, a second silicon-containing precursor anda NH₃ plasma are reacted to form a silicon oxide layer. The firstsilicon-containing precursor includes at least one of Si—H bond andSi—Si bond. The second silicon-containing precursor includes at leastone Si—N bond.

U.S. Pat. No. 7,425,350 discloses a method for making a Si-containingmaterial which comprises transporting a pyrolyzed Si-precursor to asubstrate and polymerizing the pyrolyzed Si-precursor on the substrateto form a Si-containing film. Polymerization of the pyrolyzedSi-precursor may be carried out in the presence of a porogen to therebyform a porogen-containing Si-containing film. The porogen may be removedfrom the porogen-containing, Si-containing film to thereby form a porousSi-containing film. Preferred porous Si-containing films have lowdielectric constants and thus are suitable for various low-kapplications such as in microelectronics and microelectromechanicsystems.

U.S. Pat. No. 7,888,273 discloses methods of lining and/or filling gapson a substrate by creating flowable silicon oxide-containing films areprovided. The methods involve introducing vapor-phase silicon-containingprecursor and oxidant reactants into a reaction chamber containing thesubstrate under conditions such that a condensed flowable film is formedon the substrate. The flowable film at least partially fills gaps on thesubstrates and is then converted into a silicon oxide film. In certainembodiments the methods involve using a catalyst e.g. a nucleophile oronium catalyst in the formation of the film. The catalyst may beincorporated into one of the reactants and/or introduced as a separatereactant. Also provided are methods of converting the flowable film to asolid dielectric film. The methods of this invention may be used to lineor fill high aspect ratio gaps including gaps having aspect ratiosranging from 3:1 to 10:1.

U.S. Pat. No. 7,629,227 discloses methods of lining and/or filling gapson a substrate by creating flowable silicon oxide-containing films. Themethods involve introducing vapor-phase silicon-containing precursor andoxidant reactants into a reaction chamber containing the substrate underconditions such that a condensed flowable film is formed on thesubstrate. The flowable film at least partially fills gaps on thesubstrates and is then converted into a silicon oxide film. In certainembodiments the methods involve using a catalyst e.g. a nucleophile oronium catalyst in the formation of the film. The catalyst may beincorporated into one of the reactants and/or introduced as a separatereactant. Also provided are methods of converting the flowable film to asolid dielectric film. The methods of this invention may be used to lineor fill high aspect ratio gaps including gaps having aspect ratiosranging from 3:1 to 10:1.

WO 06129773 disclosed a catalyst for polymerization of olefins formedfrom (A) a solid catalyst component containing magnesium titaniumhalogen and an electron donor compound (B) an organoaluminum compoundshown by the formula R⁶ _(p)AlQ_(3-p) and (C) an aminosilane compoundshown by the formula R³ _(n)Si(NR⁴R⁵)_(4-n); and a process for producinga catalyst for polymerization of olefins in the presence of the catalystare provided.

Thus, there is a need in the art to provide a precursor that can be usedto deposit a silicon-containing film that provides one or more of thefollowing advantages: low processing temperatures (e.g., 500° C. orbelow); a relatively good deposition rate ranging from about 0.1nanometers (nm) to 1000 nm per minute; a compositional uniformity thatdeviates by no more than ±10% measured over multiple points on a waferanalyzed by Fourier FTIR or XPS; high stability (e.g., undergoing adegradation of no more than about 5% or less per year or no more thanabout 1% or less per year); flowability for filling trenches, gap, orvias as observed by scanning electron microcopy (SEM); and combinationsthereof.

BRIEF SUMMARY OF THE INVENTION

Described herein are bisaminoalkoxysilane precursors and methods usingsame for forming stoichiometric or non-stoichiometric silicon-containingfilms, such as, but not limited to, silicon oxide, silicon carboxide,silicon nitride, silicon oxynitride, silicon carbide, siliconcarbonitride, and combinations thereof onto at least a surface orportion of a substrate. Also disclosed herein are the methods to formsilicon-containing films or coatings on an object to be processed, suchas, for example, a semiconductor wafer.

In one aspect, there is provided a composition for depositing a siliconcontaining film comprising at least one bisaminoalkoxysilane havingFormula I:R¹Si(NR²R³)(NR⁴R⁵)OR⁶  Iwhere R¹ is selected from a hydrogen atom, a C₁ to C₁₀ linear alkylgroup, a C₃ to C₁₀ branched alkyl group, a C₃ to C₁₀ cyclic alkyl group,a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynyl group, a C₄ to C₁₀aromatic hydrocarbon group; R², R³, R⁴, and R⁵ are each independentlyselected from a hydrogen atom, a C₄ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; R⁶ is selected from aC₁ to C₁₀ linear alkyl group, a C₃ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₂ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; and optionallywherein R² and R³, R⁴ and R⁵, or both in Formula I can be linkedtogether to form a ring; and optionally wherein R² and R⁴ in Formula Ican be linked together to form a diamino group. Exemplarybisaminoalkoxysilane precursor compounds having Formula I include, butare not limited to, bis(tert-butylamino)methoxymethylsilane,bis(tert-butylamino)ethoxymethylsilane,bis(cis-2,6-dimethylpiperidino)methoxymethylsilane, andbis(cis-2,6-dimethylpiperidino)ethoxymethylsilane.

In another aspect, there is provided a method for forming asilicon-containing film on at least one surface of a substratecomprising:

providing the substrate in a reactor; and

forming the silicon-containing film on the at least one surface by adeposition process using at least one precursor comprising abisaminoalkoxysilane having Formula I:R¹Si(NR²R³)(NR⁴R⁵)OR⁶  Iwhere R¹ is selected from a hydrogen atom, a C₁ to C₁₀ linear alkylgroup, a C₃ to C₁₀ branched alkyl group, a C₃ to C₁₀ cyclic alkyl group,a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynyl group, a C₄ to C₁₀aromatic hydrocarbon group; R², R³, R⁴, and R⁵ are each independentlyselected from a hydrogen atom, a C₄ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; R⁶ is selected from aC₁ to C₁₀ linear alkyl group, a C₃ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₂ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; and optionallywherein R² and R³, R⁴ and R⁵, or both in Formula I can be linkedtogether to form a ring; and optionally wherein R² and R⁴ in Formula Ican be linked together to form a diamino group.

In another aspect, there is provided a method of forming a silicon oxideor carbon doped silicon oxide film via an atomic layer depositionprocess or cyclic chemical vapor deposition process, the methodcomprising the steps of:

-   -   a. providing a substrate in a reactor;    -   b. introducing into the reactor at least one precursor        comprising a bisaminoalkoxysilane compound having Formula I:        R¹Si(NR²R³)(NR⁴R⁵)OR⁶  I        where R¹ is selected from a hydrogen atom, a C₁ to C₁₀ linear        alkyl group, a C₃ to C₁₀ branched alkyl group, a C₃ to C₁₀        cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀        alkynyl group, a C₄ to C₁₀ aromatic hydrocarbon group; R², R³,        R⁴, and R⁵ are each independently selected from a hydrogen atom,        a C₄ to C₁₀ branched alkyl group, a C₃ to C₁₀ cyclic alkyl        group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynyl group, and        a C₄ to C₁₀ aromatic hydrocarbon group; R⁶ is selected from a C₁        to C₁₀ linear alkyl group, a C₃ to C₁₀ branched alkyl group, a        C₃ to C₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₂ to        C₁₀ alkynyl group, and a C₄ to C₁₀ aromatic hydrocarbon group;        and optionally wherein R² and R³, R⁴ and R⁵, or both in Formula        I can be linked together to form a ring; and optionally wherein        R² and R⁴ in Formula I can be linked together to form a diamino        group;    -   c. purging the reactor with a purge gas;    -   d. introducing an oxygen source into the reactor;    -   e. purging the reactor with a purge gas; and        repeating the steps b through e until a desired thickness of the        film is obtained.

In a further aspect, there is provided a method of forming a siliconoxide or carbon doped silicon oxide film onto at least a surface of asubstrate using a CVD process comprising:

-   -   a. providing a substrate in a reactor;    -   b. introducing into the reactor at least one precursor        comprising a bisaminoalkoxysilane compound having the following        Formula I:        R¹Si(NR²R³)(NR⁴R⁵)OR⁶  I        where R¹ is selected from a hydrogen atom, a C₁ to C₁₀ linear        alkyl group, a C₃ to C₁₀ branched alkyl group, a C₃ to C₁₀        cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀        alkynyl group, a C₄ to C₁₀ aromatic hydrocarbon group; R², R³,        R⁴, and R⁵ are each independently selected from a hydrogen atom,        a C₄ to C₁₀ branched alkyl group, a C₃ to C₁₀ cyclic alkyl        group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynyl group, and        a C₄ to C₁₀ aromatic hydrocarbon group; R⁶ is selected from a C₁        to C₁₀ linear alkyl group, a C₃ to C₁₀ branched alkyl group, a        C₃ to C₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₂ to        C₁₀ alkynyl group, and a C₄ to C₁₀ aromatic hydrocarbon group;        and optionally wherein R² and R³, R⁴ and R⁵, or both in Formula        I can be linked together to form a ring; and optionally wherein        R² and R⁴ in Formula I can be linked together to form a diamino        group; and    -   c. providing an oxygen source to deposit the silicon oxide or        carbon doped silicon oxide film onto the at least one surface.

In another aspect, there is provided a method of forming a siliconnitride or silicon oxynitride or silicon carboxynitride film via anatomic layer deposition process or cyclic chemical vapor depositionprocess, the method comprising the steps of:

-   -   a. providing a substrate in a reactor;    -   b. introducing into the reactor an at least one precursor        comprising a bisaminoalkoxysilane compound having Formula I:        R¹Si(NR²R³)(NR⁴R⁵)OR⁶  I        where R¹ is selected from a hydrogen atom, a C₁ to C₁₀ linear        alkyl group, a C₃ to C₁₀ branched alkyl group, a C₃ to C₁₀        cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀        alkynyl group, a C₄ to C₁₀ aromatic hydrocarbon group; R², R³,        R⁴, and R⁵ are each independently selected from a hydrogen atom,        a C₄ to C₁₀ branched alkyl group, a C₃ to C₁₀ cyclic alkyl        group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynyl group, and        a C₄ to C₁₀ aromatic hydrocarbon group; R⁶ is selected from a C₁        to C₁₀ linear alkyl group, a C₃ to C₁₀ branched alkyl group, a        C₃ to C₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₂ to        C₁₀ alkynyl group, and a C₄ to C₁₀ aromatic hydrocarbon group;        and optionally wherein R² and R³, R⁴ and R⁵, or both in Formula        I can be linked together to form a ring; and optionally wherein        R² and R⁴ in Formula I can be linked together to form a diamino        group;    -   c. purging the reactor with a purge gas;    -   d. introducing a nitrogen-containing source into the reactor;    -   e. purging the reactor with a purge gas; and        repeating the steps b through e until a desired thickness of the        silicon nitride or silicon oxynitride or silicon carboxynitride        film is obtained.

In a further aspect, there is provided a method of forming a siliconnitride or silicon oxynitride film onto at least a surface of asubstrate using a CVD process comprising:

-   -   a. providing a substrate in a reactor;    -   b. introducing into the reactor at least one precursor        comprising a bisaminoalkoxysilane compound having Formula I:        R¹Si(NR²R³)(NR⁴R⁵)OR⁶  I        where R¹ is selected from a hydrogen atom, a C₁ to C₁₀ linear        alkyl group, a C₃ to C₁₀ branched alkyl group, a C₃ to C₁₀        cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀        alkynyl group, a C₄ to C₁₀ aromatic hydrocarbon group; R², R³,        R⁴, and R⁵ are each independently selected from a hydrogen atom,        a C₄ to C₁₀ branched alkyl group, a C₃ to C₁₀ cyclic alkyl        group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynyl group, and        a C₄ to C₁₀ aromatic hydrocarbon group; R⁶ is selected from a C₁        to C₁₀ linear alkyl group, a C₃ to C₁₀ branched alkyl group, a        C₃ to C₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₂ to        C₁₀ alkynyl group, and a C₄ to C₁₀ aromatic hydrocarbon group;        and optionally wherein R² and R³, R⁴ and R⁵, or both in Formula        I can be linked together to form a ring; and optionally wherein        R² and R⁴ in Formula I can be linked together to form a diamino        group; and    -   c. providing a nitrogen-containing source wherein the at least        one bisaminoalkoxysilane precursors and the nitrogen-containing        source react to deposit the film comprising both silicon and        nitrogen onto the at least one surface.

In another aspect, a vessel for depositing a silicon-containing filmcomprising one or more bisaminoalkoxysilane precursor compound havingFormula I is described herein. In one particular embodiment, the vesselcomprises at least one pressurizable vessel (preferably of stainlesssteel) fitted with the proper valves and fittings to allow the deliveryof one or more precursors to the reactor for a CVD or an ALD process.

In yet another aspect, there is provided a composition for thedeposition of a silicon-containing film comprising: at least oneprecursor comprising a bisaminoalkoxysilane compound having thefollowing Formula I:R¹Si(NR²R³)(NR⁴R⁵)OR⁶  Iwhere R¹ is selected from a hydrogen atom, a C₁ to C₁₀ linear alkylgroup, a C₃ to C₁₀ branched alkyl group, a C₃ to C₁₀ cyclic alkyl group,a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynyl group, a C₄ to C₁₀aromatic hydrocarbon group; R², R³, R⁴, and R⁵ are each independentlyselected from a hydrogen atom, a C₄ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; R⁶ is selected from aC₁ to C₁₀ linear alkyl group, a C₃ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₂ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; and optionallywherein R² and R³, R⁴ and R⁵, or both in Formula I can be linkedtogether to form a ring; and optionally wherein R² and R⁴ in Formula Ican be linked together to form a diamino group.

DETAILED DESCRIPTION OF THE INVENTION

Bisaminoalkoxysilane compounds are used as precursors to depositstoichiometric and non-stoichiometric silicon containing films such as,but not limited to, silicon oxide, silicon oxycarbide, silicon nitride,silicon oxynitride and silicon oxycarbonitride using a variety ofdeposition processes. The bisaminoalkoxysilane precursors describedherein are high purity (e.g., ranging from about 90% to about 99.9 orabout 95% to 99% assay as measured by gas chromatography (GC)), volatileliquid precursors.

The precursors are typically vaporized and delivered to a depositionchamber or reactor as a gas to deposit a silicon containing film viavarious deposition techniques including, but not limited to, chemicalvapor deposition (CVD), cyclic chemical vapor deposition (CCVD), plasmaenhanced chemical vapor deposition (PECVD), flowable chemical vapordeposition (FCVD), atomic layer deposition (ALD), and plasma enhancedatomic layer deposition (PEALD) in the manufacture of a semiconductordevice. In other embodiments, the bisaminoalkoxysilanes precursors canbe used in a liquid-based deposition or film formation method such as,but not limited to, spin-on, dip coat, aerosol, ink jet, screen printingor spray application. The selection of a precursor material fordeposition depends upon the desired resultant dielectric material orfilm. For example, a precursor material may be chosen for its content ofchemical elements, its stoichiometric ratio of chemical elements, and/orthe resultant silicon-containing film or coating that is formed underthe aforementioned deposition processes. The precursor material may alsobe chosen for one or more of the following characteristics: cost,non-toxicity, handling characteristics, ability to maintain liquid phaseat room temperature, volatility, molecular weight, and/or otherconsiderations. In certain embodiments, the precursors described hereincan be delivered to the reactor system by any number of means,preferably using a pressurizable stainless steel vessel fitted with theproper valves and fittings, to allow the delivery of the liquid phaseprecursor to the deposition chamber or reactor.

It is believed that the bisaminoalkoxysilane precursors described hereinmay provide better reactivity towards substrate surface during chemicalvapor deposition or atomic layer deposition because the precursors haveat least one or more of the bonds, Si—N, Si—O, optionally Si—H, andoptionally Si—NH, which allow them to chemically react on substratesurfaces during a vapor deposition process. It is believed that thebisaminoalkoxysilane precursors described herein may provide betterreactivity towards the substrate surface during chemical vapordeposition, particularly cyclic CVD deposition, or ALD, to form aSi—N—Si linkage or a Si—O—Si linkage due to these bonds. In addition tothe foregoing advantages, in certain embodiments such as for depositinga silicon oxide or silicon nitride film using a cyclic CVD, an ALD, orPEALD deposition method, the bisaminoalkoxysilane precursor describedherein may be able to deposit high density materials at relatively lowdeposition temperatures, e.g., at 500° C. or less, at 400° C. or less,or at 300° C. or less. In other embodiments, the precursors describedherein can be used, for example, in higher temperature deposition attemperatures ranging from about 500° C. to about 800° C.

Without being bound by theory, it is believed that the compoundsdescribed herein overcome the problems associated with other precursorsin the prior art by having substituents or ligands with varying relativereactivity. In this connection, the compounds contain silicon-aminesubstituent groups which are highly reactive and prone to react with aprotic reagent such as, without limitation, water in a rapid fashion.This feature allows the precursor to rapidly deposit a flowable filmunder capillary co-condensation conditions between the precursor, proticreagent, and optional co-solvent. In order to prevent the rapid reactionfrom causing premature solidification, one can limit the number ofhighly reactive substituent groups to no more than two per silicon atom,meaning that a three-dimensional networked polymer, which will quicklysolidify, cannot form until the remaining, more slowly reactivesubstituent groups are reacted. An example of this is shown in thefollowing Scheme A wherein the compound having Formula I containsR¹=methyl (Me), R²═R⁴=hydrogen, R³═R⁵=tert-butyl (But), R⁶=Me, n=aninteger from 3 to 1000, and m=an integer from 4 to 1,000. As Scheme Ashows, the tert-butyl amino substituent group reacts quickly, or withinseconds of contact with water, whereas the methyl hydroxyl substituentgroup reacts relatively slowly, compared to the tert-butyl aminosubstituent group, or within minutes to hours of contact with water.

In one embodiment, described herein are deposition processes usingbisaminoalkoxysilane compounds having the following Formula I:R¹Si(NR²R³)(NR⁴R⁵)OR⁶  Iwhere R¹ is selected from a hydrogen atom, a C₁ to C₁₀ linear alkylgroup, a C₃ to C₁₀ branched alkyl group, a C₃ to C₁₀ cyclic alkyl group,a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynyl group, a C₄ to C₁₀aromatic hydrocarbon group; R², R³, R⁴, and R⁵ are each independentlyselected from a hydrogen atom, a C₄ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; R⁶ is selected from aC₁ to C₁₀ linear alkyl group, a C₃ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₂ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; and optionallywherein R² and R³, R⁴ and R⁵, or both in Formula I can be linkedtogether to form a ring; and optionally wherein R² and R⁴ in Formula Ican be linked together to form a diamino group.

In one particular embodiment of Formula I, R² and R⁴ are both hydrogenatoms and R³ and R⁵ are independently selected from a C₄ to C₁₀ branchedalkyl group, such as a tert-butyl or tert-pentyl group. Without beingbound by any particular theory, it is believed that steric hindrance ofthe branched alkyl group provides better thermal stability. The term“stable” as used herein means that the precursor described herein doesnot change 0.5 weight (wt) % or greater, 1 wt % or greater, 2 wt % orgreater, 5 wt % or greater, or 10 wt % or greater from its initialcomposition after being stored for a time period of six (6) months orgreater, one (1) year or greater, two (2) years or greater or such othertime period which is indicative of being shelf stable. For example, theconcentration of the precursor should not compositionally change by morethan 10% of its initial percentage based on gas chromatography (GC) orother analytical techniques after storage for 1 year in order to beconsidered stable as described herein. Good thermal and compositionalstability of the precursor is important to ensure consistent precursordelivery to a vapor deposition chamber and consistent vapor depositionparameters. In addition, good thermal stability also reduces the chancefor substituent or ligand exchange during storage and handling.

In Formula I and throughout the description, the term “linear alkyl”denotes a linear functional group having from 1 to 10 or 1 to 4 carbonatoms. Exemplary linear alkyl groups include, but are not limited to,methyl, ethyl, n-propyl, n-butyl, n-pentyl, and hexyl groups. In FormulaI and throughout the description, the term “branched alkyl” denotes abranched functional group having from 3 to 10 or 4 to 6 carbon atoms.Exemplary alkyl groups include, but are not limited to, isopropyl,isobutyl, sec-butyl, tert-butyl, iso-pentyl, tert-pentyl, and isohexyl.In certain embodiments, the alkyl group may have one or more functionalgroups such as, but not limited to, an alkoxy group, a dialkylaminogroup or combinations thereof, attached thereto. In other embodiments,the alkyl group does not have one or more functional groups attachedthereto.

In Formula I and throughout the description, the term “cyclic alkyl”denotes a cyclic functional group having from 3 to 10 or from 4 to 10carbon atoms. Exemplary cyclic alkyl groups include, but are not limitedto, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

In Formula I and throughout the description, the term “aromatichydrocarbon” denotes an aromatic cyclic functional group having from 4to 10 carbon atoms. Exemplary aryl groups include, but are not limitedto, phenyl, benzyl, chlorobenzyl, tolyl, and o-xylyl. In certainembodiments, the aromatic hydrocarbon group has one or more functionalgroups.

In Formula I and throughout the description, the term “alkenyl group”denotes a group which has one or more carbon-carbon double bonds and hasfrom 3 to 10 or from 2 to 6 carbon atoms. Exemplary alkenyl groupsinclude, but are not limited to, vinyl or allyl groups

In Formula I and throughout the description, the term “alkynyl group”denotes a group which has one or more carbon-carbon triple bonds and hasfrom 3 to 10 or from 2 to 6 carbon atoms.

In Formula I and throughout the description, the term “alkoxy” denotesan alkyl group which has is linked to an oxygen atom (e.g., R—O) and mayhave from 1 to 12, or from 1 to 6 carbon atoms. Exemplary alkoxy groupsinclude, but are not limited to, methoxy (—OCH₃), ethoxy(—OCH₂CH₃),n-propoxy (—OCH₂CH₂CH₃), and iso-propoxy (—OCHMe₂).

In certain embodiments, one or more of the alkyl group, alkenyl group,alkynyl group, alkoxy group, and/or aryl group in Formula I may besubstituted or have one or more atoms or group of atoms substituted inplace of, for example, a hydrogen atom. Exemplary substituents include,but are not limited to, oxygen, sulfur, halogen atoms (e.g., F, Cl, I,or Br), nitrogen, and phosphorous. In one particular embodiment, thealkyl group in Formula I may comprise oxygen or nitrogen. In otherembodiments, one or more of the alkyl group, alkenyl group, alkynylgroup, alkoxy group, and/or aryl in Formula I may be unsubstituted.

Examples of the bisaminoalkoxysilane of Formula I described hereininclude, but are not limited to,bis(tert-butylamino)methoxymethylsilane,bis(tert-butylamino)ethoxymethylsilane,bis(cis-2,6-dimethylpiperidino)methoxymethylsilane, andbis(cis-2,6-dimethylpiperidino)ethoxymethylsilane.

In certain embodiments of the invention described herein, thebisaminoalkoxysilane precursor having the above Formula I can becombined with one or more silicon-containing precursors selected fromthe group consisting of dialkylaminosilanes, alkoxysilanes,dialkylaminoalkylsilanes, and alkoxyalkylsilanes to provide acomposition for depositing a silicon-containing film. In theseembodiments, the composition comprises an bisaminoalkoxysilane havingFormula I and a silicon-containing precursor. Examples ofsilicon-containing precursors for these compositions include, but notlimited to, bis(tert-butylamino)silane (BTBAS),tris(dimethylamino)silane (TRDMAS), tetraethoxysilane (TEOS),triethoxysilane (TES), di-tert-butoxysilane (DTBOS),di-tert-pentoxysilane (DTPOS), methyltriethoxysilane (MTES),tetramethoxysilane (TMOS), trimethoxysilane (TMOS),methyltrimethoxysilane (MTMOS), di-tert-butoxymethylsilane,di-tert-butoxyethylsilane, di-tert-pentoxymethylsilane, anddi-tert-pentoxyethylsilane.

Examples of compositions comprising silicon-containing precursor and abisaminoalkoxysilane of Formula I include, but are not limited to,tetraethoxysilane (TEOS) and di-ethoxy(tert-butylamino)silane,tetraethoxysilane (TEOS) and diethoxy(tert-pentylamino)silane,tetraethoxysilane (TEOS) and diethoxy(iso-propoxyamino)silane,triethoxysilane (TES) and diethoxy(tert-butylamino)silane,triethoxysilane (TES) and diethoxy(tert-pentylamino)silane,triethoxysilane (TES) and diethoxy(iso-propoxyamino)silane,di-tert-butoxysilane (DTBOS) and di-tert-butoxy(methylamino)silane,di-tert-butoxysilane (DTBOS) and di-tert-butoxy(ethylamino)silane,di-tert-butoxysilane (DTBOS) and di-tert-butoxy(iso-propylamino)silane,di-tert-butoxysilane (DTBOS) and di-tert-butoxy(n-butylamino)silane,di-tert-butoxysilane (DTBOS) and di-tert-butoxy(sec-butylamino)silane,di-tert-butoxysilane (DTBOS) and di-tert-butoxy(iso-butylamino)silane,di-tert-butoxysilane (DTBOS) and di-tert-butoxy(tert-butylamino)silane,di-tert-pentoxysilane (DTPOS) and di-tert-pentoxy(methylamino)silane,di-tert-pentoxysilane (DTPOS) and di-tert-pentoxy(ethylamino)silane,di-tert-pentoxysilane (DTPOS) anddi-tert-pentoxy(iso-propylamino)silane, di-tert-pentoxysilane (DTPOS)and di-tert-pentoxy(n-butylamino)silane, di-tert-pentoxysilane (DTPOS)and di-tert-pentoxy(sec-butylamino)silane, di-tert-pentoxysilane (DTPOS)and di-tert-pentoxy(iso-butylamino)silane, di-tert-pentoxysilane (DTPOS)and di-tert-pentoxy(tert-butylamino)silane. In one particularembodiment, the composition is used to deposit a silicon oxide film byflowable chemical vapor deposition wherein the bisaminoalkoxysilanehaving Formula I acts as a catalyst. In this or other embodiments, thesilicon-containing precursor is selected to be compatible with thebisaminoalkoxysilane by having, for example, the same alkoxysubstituent.

As previously mentioned, the deposition method used to form thesilicon-containing films or coatings are deposition processes. Examplesof suitable deposition processes for the method disclosed hereininclude, but are not limited to, cyclic CVD

(CCVD), thermal chemical vapor deposition, plasma enhanced chemicalvapor deposition (PECVD), high density PECVD, photon assisted CVD,plasma-photon assisted (PPECVD), cryogenic chemical vapor deposition,chemical assisted vapor deposition, hot-filament chemical vapordeposition, CVD of a liquid polymer precursor, and low energy CVD(LECVD), and flowable chemical vapor deposition (FCVD).

In one particular embodiment, such as for depositing a silicon oxideusing typical FCVD processes, the bisaminoalkoxysilane precursordescribed herein may be used in combination with othersilicon-containing precursors such as those compositions describedherein as a catalyst due to release of organoamine as an in situcatalyst at relatively low deposition temperatures, e.g., at 100° C. orless, 50° C. or less, 20° C. or less, even 0° C. or lower.

As used herein, the term “chemical vapor deposition processes” refers toany process wherein a substrate is exposed to one or more volatileprecursors, which react and/or decompose on the substrate surface toproduce the desired deposition.

As used herein, the term “atomic layer deposition process” refers to aself-limiting (e.g., the amount of film material deposited in eachreaction cycle is constant), sequential surface chemistry that depositsfilms of materials onto substrates of varying compositions. In oneembodiment, the film is deposited via an ALD process by exposing thesubstrate surface alternatively to the one or more thesilicon-containing precursor, oxygen source, nitrogen-containing source,or other precursor or reagent. Film growth proceeds by self-limitingcontrol of surface reaction, the pulse length of each precursor orreagent, and the deposition temperature. However, once the surface ofthe substrate is saturated, the film growth ceases.

Although the precursors, reagents and sources used herein may besometimes described as “gaseous”, it is understood that the precursorscan be either liquid or solid which are transported with or without aninert gas into the reactor via direct vaporization, bubbling orsublimation. In some case, the vaporized precursors can pass through aplasma generator.

The term “reactor” as used herein, includes without limitation, reactionchamber or deposition chamber.

Depending upon the deposition method, in certain embodiments,bisaminoalkoxysilane precursors with Formula I, other silicon-containingprecursors may be introduced into the reactor at a predetermined molarvolume, or from about 0.1 to about 1000 micromoles. In this or otherembodiments, the bisaminoalkoxysilane precursor may be introduced intothe reactor for a predetermined time period. In certain embodiments, thetime period ranges from about 0.001 to about 500 seconds.

In certain embodiments, the silicon-containing films deposited using themethods described herein are formed in the presence of oxygen using anoxygen source, reagent or precursor comprising oxygen.

An oxygen source may be introduced into the reactor in the form of atleast one oxygen source and/or may be present incidentally in the otherprecursors used in the deposition process.

Suitable oxygen source gases may include, for example, water (H₂O)(e.g., deionized water, purifier water, and/or distilled water, amixture containing water and other organic liquid), oxygen (O₂), oxygenplasma, ozone (O₃), NO, NO₂, carbon monoxide (CO), hydrogen peroxide, acomposition comprising hydrogen and oxygen, carbon dioxide (CO₂) andcombinations thereof. The organic liquid in the mixture can be selectedfrom hydrocarbon, aromatic hydrocarbon, ether, amine, ketone, ester,alcohols, organic acid, diols, acetylenic alcohols and organic amide.

In certain embodiments, the oxygen source comprises an oxygen source gasthat is introduced into the reactor at a flow rate ranging from about 1to about 2000 square cubic centimeters (sccm) or from about 1 to about1000 sccm. The oxygen source can be introduced for a time that rangesfrom about 0.1 to about 100 seconds.

In one particular embodiment, the oxygen source comprises water having atemperature of 10° C. or greater.

In embodiments wherein the film is deposited by an ALD or a cyclic CVDprocess, the precursor pulse can have a pulse duration that is greaterthan 0.01 seconds, and the oxygen source can have a pulse duration thatis less than 0.01 seconds, while the water pulse duration can have apulse duration that is less than 0.01 seconds.

In yet another embodiment, the purge duration between the pulses thatcan be as low as 0 seconds or is continuously pulsed without a purgein-between. The oxygen source or reagent is provided in a molecularamount less than a 1:1 ratio to the silicon precursor, so that at leastsome carbon is retained in the as deposited silicon-containing film.

In certain embodiments, oxygen source is continuously flowing into thereactor while precursor pulse and plasma are introduced in sequence. Theprecursor pulse can have a pulse duration greater than 0.01 secondswhile the plasma duration can range between 0.01 seconds to 100 seconds.

In certain embodiments, the silicon-containing films comprise siliconand nitrogen. In these embodiments, the silicon-containing filmsdeposited using the methods described herein are formed in the presenceof nitrogen-containing source. An nitrogen-containing source may beintroduced into the reactor in the form of at least one nitrogen sourceand/or may be present incidentally in the other precursors used in thedeposition process.

Suitable nitrogen-containing source gases may include, for example,ammonia, hydrazine, monoalkylhydrazine, symmetrical or unsymmetricaldialkylhydrazine, nitrogen, NO, N₂O, NO₂, nitrogen/hydrogen, ammoniaplasma, nitrogen plasma, ammonia/nitrogen plasma, nitrogen/hydrogenplasma, an organoamine plasma, and mixture thereof. In embodimentswherein an organoamine plasma is used as a nitrogen-containing source,exemplary organic amine plasmas included, are not limited to,diethylamine plasma, dimethylamine plasma, trimethyl plasma,trimethylamine plasma, ethylenediamine plasma, and an alkoxyamine suchas ethanolamine plasma.

In certain embodiments, the nitrogen-containing source comprises anammonia plasma or a plasma source gas comprising hydrogen and nitrogenthat is introduced into the reactor at a flow rate ranging from about 1to about 2000 square cubic centimeters (sccm) or from about 1 to about1000 sccm.

The nitrogen-containing source can be introduced for a time that rangesfrom about 0.1 to about 100 seconds. In embodiments wherein the film isdeposited by an ALD or a cyclic CVD process, the precursor pulse canhave a pulse duration that is greater than 0.01 seconds, and thenitrogen-containing source can have a pulse duration that is less than0.01 seconds, while the water pulse duration can have a pulse durationthat is less than 0.01 seconds. In yet another embodiment, the purgeduration between the pulses that can be as low as 0 seconds or iscontinuously pulsed without a purge in-between.

The deposition methods disclosed herein may involve one or more purgegases. The purge gas, which is used to purge away unconsumed reactantsand/or reaction byproducts, is an inert gas that does not react with theprecursors. Exemplary purge gases include, but are not limited to, argon(Ar), nitrogen (N₂), helium (He), neon, hydrogen (H₂), and mixturesthereof. In certain embodiments, a purge gas such as Ar is supplied intothe reactor at a flow rate ranging from about 10 to about 2000 sccm forabout 0.1 to 1000 seconds, thereby purging the unreacted material andany byproduct that may remain in the reactor.

The respective step of supplying the precursors, oxygen source, thenitrogen-containing source, and/or other precursors, source gases,and/or reagents may be performed by changing the time for supplying themto change the stoichiometric composition of the resulting film.

Energy is applied to the at least one of the precursor,nitrogen-containing source, reducing agent, other precursors orcombination thereof to induce reaction and to form the film or coatingon the substrate. Such energy can be provided by, but not limited to,thermal, plasma, pulsed plasma, helicon plasma, high density plasma,inductively coupled plasma, X-ray, e-beam, photon, remote plasmamethods, and combinations thereof.

In certain embodiments, a secondary RF frequency source can be used tomodify the plasma characteristics at the substrate surface. Inembodiments wherein the deposition involves plasma, the plasma-generatedprocess may comprise a direct plasma-generated process in which plasmais directly generated in the reactor, or alternatively a remoteplasma-generated process in which plasma is generated outside of thereactor and supplied into the reactor.

The bisaminoalkoxysilane precursors and/or other silicon-containingprecursors may be delivered to the reaction chamber, such as a CVD orALD reactor, in a variety of ways. In one embodiment, a liquid deliverysystem may be utilized. In an alternative embodiment, a combined liquiddelivery and flash vaporization process unit may be employed, such as,for example, the turbo vaporizer manufactured by MSP Corporation ofShoreview, Minn., to enable low volatility materials to bevolumetrically delivered, which leads to reproducible transport anddeposition without thermal decomposition of the precursor. In liquiddelivery formulations, the precursors described herein may be deliveredin neat liquid form, or alternatively, may be employed in solventformulations or compositions comprising same. Thus, in certainembodiments the precursor formulations may include solvent component(s)of suitable character as may be desirable and advantageous in a givenend use application to form a film on a substrate.

In this or other embodiments, it is understood that the steps of themethods described herein may be performed in a variety of orders, may beperformed sequentially or concurrently (e.g., during at least a portionof another step), and any combination thereof. The respective step ofsupplying the precursors and the nitrogen-containing source gases may beperformed by varying the duration of the time for supplying them tochange the stoichiometric composition of the resultingsilicon-containing film.

In another embodiment of the method disclosed herein, silicon-containingfilms are formed using an ALD deposition method that comprises the stepsof:

providing a substrate in an ALD reactor;

introducing into the ALD reactor at least one precursor comprising anbisaminoalkoxysilane compounds having a Formula I:R¹Si(NR²R³)(NR⁴R⁵)OR⁶  Iwhere R¹ is selected from a hydrogen atom, a C₁ to C₁₀ linear alkylgroup, a C₃ to C₁₀ branched alkyl group, a C₃ to C₁₀ cyclic alkyl group,a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynyl group, a C₄ to C₁₀aromatic hydrocarbon group; R², R³, R⁴, and R⁵ are each independentlyselected from a hydrogen atom, a C₄ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; R⁶ is selected from aC₁ to C₁₀ linear alkyl group, a C₃ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₂ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; and optionallywherein R² and R³, R⁴ and R⁵, or both in Formula I can be linkedtogether to form a ring; and optionally wherein R² and R⁴ in Formula Ican be linked together to form a diamino group;

chemisorbing the at least one bisaminoalkoxysilane precursor onto asubstrate;

purging away the unreacted at least one bisaminoalkoxysilane precursorusing a purge gas;

providing a nitrogen-containing source to the at least onebisaminoalkoxysilane precursor onto the heated substrate to react withthe sorbed at least one bisaminoalkoxysilane precursor; and

optionally purging away any unreacted nitrogen-containing source.

In another embodiment of the method disclosed herein, thesilicon-containing films are formed using an ALD deposition method thatcomprises the steps of:

providing a substrate in a reactor;

introducing into the reactor an at least one precursor comprising anbisaminoalkoxysilane compounds having a Formula (I):R¹Si(NR²R³)(NR⁴R⁵)OR⁶  Iwhere R¹ is selected from a hydrogen atom, a C₁ to C₁₀ linear alkylgroup, a C₃ to C₁₀ branched alkyl group, a C₃ to C₁₀ cyclic alkyl group,a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynyl group, a C₄ to C₁₀aromatic hydrocarbon group; R², R³, R⁴, and R⁵ are each independentlyselected from a hydrogen atom, a C₄ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; R⁶ is selected from aC₁ to C₁₀ linear alkyl group, a C₃ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₂ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; and optionallywherein R² and R³, R⁴ and R⁵, or both in Formula I can be linkedtogether to form a ring; and optionally wherein R² and R⁴ in Formula Ican be linked together to form a diamino group;

chemisorbing the at least one bisaminoalkoxysilane precursor onto asubstrate;

purging away the unreacted at least one bisaminoalkoxysilane precursorusing a purge gas;

providing an oxygen source to the at least one bisaminoalkoxysilaneprecursor onto the heated substrate to react with the sorbed at leastone bisaminoalkoxysilane precursor; and

optionally purging away any unreacted oxygen source.

The above steps define one cycle for the method described herein; andthe cycle can be repeated until the desired thickness of asilicon-containing film is obtained. In this or other embodiments, it isunderstood that the steps of the methods described herein may beperformed in a variety of orders, may be performed sequentially orconcurrently (e.g., during at least a portion of another step), and anycombination thereof. The respective step of supplying the precursors andoxygen source may be performed by varying the duration of the time forsupplying them to change the stoichiometric composition of the resultingsilicon-containing film, although always using oxygen in less than astoichiometric amount relative to the available silicon. Formulti-component silicon-containing films, other precursors such assilicon-containing precursors, nitrogen-containing precursors, reducingagents, or other reagents can be alternately introduced into the reactorchamber.

In a further embodiment of the method described herein, the silicon andoxide containing film is deposited using a thermal CVD process. In thisembodiment, the method comprises:

placing one or more substrates into a reactor which is heated to atemperature ranging from ambient temperature to about 700° C. andmaintained at a pressure of 10 Torr or less;

introducing at least one precursor comprising a bisaminoalkoxysilanecompounds having a Formula I:R¹Si(NR²R³)(NR⁴R⁵)OR⁶  Iwhere R¹ is selected from a hydrogen atom, a C₁ to C₁₀ linear alkylgroup, a C₃ to C₁₀ branched alkyl group, a C₃ to C₁₀ cyclic alkyl group,a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynyl group, a C₄ to C₁₀aromatic hydrocarbon group; R², R³, R⁴, and R⁵ are each independentlyselected from a hydrogen atom, a C₄ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; R⁶ is selected from aC₁ to C₁₀ linear alkyl group, a C₃ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₂ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; and optionallywherein R² and R³, R⁴ and R⁵, or both in Formula I can be linkedtogether to form a ring; and optionally wherein R² and R⁴ in Formula Ican be linked together to form a diamino group; and

providing an oxygen source into the reactor to at least partially reactwith the at least one bisaminoalkoxysilane precursor and deposit thefilm onto the one or more substrates. In certain embodiments of the CVDmethod, the reactor is maintained at a pressure ranging from 100 mTorrto 10 Torr during the introducing step.

The above steps define one cycle for the method described herein; andthe cycle can be repeated until the desired thickness of asilicon-containing film is obtained. In this or other embodiments, it isunderstood that the steps of the methods described herein may beperformed in a variety of orders, may be performed sequentially orconcurrently (e.g., during at least a portion of another step), and anycombination thereof. The respective step of supplying the precursors andoxygen source may be performed by varying the duration of the time forsupplying them to change the stoichiometric composition of the resultingsilicon-containing film, although always using oxygen in less than astoichiometric amount relative to the available silicon. Formulti-component silicon-containing films, other precursors such assilicon-containing precursors, nitrogen-containing precursors, oxygensources, reducing agents, and/or other reagents can be alternatelyintroduced into the reactor chamber.

In a further embodiment of the method described herein, the silicon andnitride containing film is deposited using a thermal CVD process. Inthis embodiment, the method comprises:

placing one or more substrates into a reactor which is heated to atemperature ranging from ambient temperature to about 700° C. andmaintained at a pressure of 10 Torr or less;

introducing at least one precursor comprising a bisaminoalkoxysilanecompound having a Formula I:R¹Si(NR²R³)(NR⁴R⁵)OR⁶  Iwhere R¹ is selected from a hydrogen atom, a C₁ to C₁₀ linear alkylgroup, a C₃ to C₁₀ branched alkyl group, a C₃ to C₁₀ cyclic alkyl group,a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynyl group, a C₄ to C₁₀aromatic hydrocarbon group; R², R³, R⁴, and R⁵ are each independentlyselected from a hydrogen atom, a C₄ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; R⁶ is selected from aC₁ to C₁₀ linear alkyl group, a C₃ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₂ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; and optionallywherein R² and R³, R⁴ and R⁵, or both in Formula I can be linkedtogether to form a ring; and optionally wherein R² and R⁴ in Formula Ican be linked together to form a diamino group; and

providing a nitrogen-containing source into the reactor to at leastpartially react with the at least one bisaminoalkoxysilane precursor anddeposit a silicon-containing film onto the one or more substrates. Incertain embodiments of the CVD method, the reactor is maintained at apressure ranging from 100 mTorr to 10 Torr during the introducing step.

As previously mentioned, the process described herein can be used todeposit a film using more than one precursor such as thebisaminoalkoxysilane compound having Formula I described herein with anadditional precursor such as another silicon-containing precursor suchas those described herein. In these embodiments, the one or moreprecursors are described as a first precursor, a second precursor, athird precursor, etc. depending upon the number of different precursorsused. The process can be used, for example, in a cyclic chemical vapordeposition or an atomic layer deposition. In these or other embodiments,the precursors can be introduced in a variety of ways (e.g., a.introduce first precursor; b. purge; c. introduce second precursor; d.purge; e. introduce third precursor; f. purge, etc., or, alternatively,a. introduce first precursor; b. purge; c. introduce second precursor;d. purge; e. introduce second precursor; etc.) In one particularembodiment, there is provided a process to deposit a silicon-containingfilm comprising the following steps:

a. Contacting vapors generated from a first precursor with a heatedsubstrate to chemically sorb the first precursor on the heatedsubstrate;

b. Purging away any unsorbed precursors;

c. Introducing an oxygen source on the heated substrate to react withthe sorbed first precursor;

d. Purging away any unreacted oxygen source;

e. Contacting vapors generated from a second precursor which isdifferent from the first precursor with a heated substrate to chemicallysorb the second precursor on the heated substrate;

f. Purging away any unsorbed precursors;

g. Introducing an oxygen source on the heated substrate to react withthe sorbed first and second precursors; and

h. Purging away any unreacted oxygen source wherein steps a. through h.are repeated until a desired thickness has been reached.

In a yet another embodiment of the process described herein, there isprovided a method of depositing a silicon-containing film comprising thefollowing steps:

a. Contacting vapors generated from a first precursor with a heatedsubstrate to chemically sorb the first precursors on the heatedsubstrate;

b. Purging away any unsorbed first precursors;

c. Introducing a nitrogen source on the heated substrate to react withthe sorbed first precursor;

d. Purging away any unreacted nitrogen source;

e. Contacting vapors generated from a second precursor which isdifferent from the first with a heated substrate to chemically sorb thesecond precursor on the heated substrate;

f. Purging away any unsorbed second precursors;

g. Introducing a nitrogen source on the heated substrate to react withthe sorbed second precursor; and

h. Purging away any unreacted nitrogen source

wherein steps a. through h. are repeated until a desired thickness offilm has been reached.

In another embodiment, there is described a method for depositing asilicon-containing film in a flowable chemical vapor deposition processwherein the substrate has at least one surface feature. The term“surface feature” as used herein means a feature such as, withoutlimitation, pore, trench, well, step, gap, via, and combination thereof.

In one particular embodiment, the flowable chemical vapor depositionprocess comprises the steps of:

placing a substrate having a surface feature into a reactor which aremaintained at a temperature ranging from −20° C. to about 400° C.;

introducing into the reactor at least one precursor comprising abisaminoalkoxysilane compounds having a Formula I:R¹Si(NR²R³)(NR⁴R⁵)OR⁶  Iwhere R¹ is selected from a hydrogen atom, a C₁ to C₁₀ linear alkylgroup, a C₃ to C₁₀ branched alkyl group, a C₃ to C₁₀ cyclic alkyl group,a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynyl group, a C₄ to C₁₀aromatic hydrocarbon group; R², R³, R⁴, and R⁵ are each independentlyselected from a hydrogen atom, a C₄ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; R⁶ is selected from aC₁ to C₁₀ linear alkyl group, a C₃ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₂ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; and optionallywherein R² and R³, R⁴ and R⁵, or both in Formula I can be linkedtogether to form a ring; and optionally wherein R² and R⁴ in Formula Ican be linked together to form a diamino group and a nitrogen sourcewherein the at least one compound reacts with the nitrogen source toform a nitride containing film on at least a portion of the surfacefeature; and

treating the substrate with an oxygen source at one or more temperaturesranging from about 100° C. to about 1000° C. to form the film on atleast a portion of the surface feature. In an alternative embodiment,the film may be exposed to an oxygen source while being exposed to UVirradiation at temperatures ranging from about 100° C. to about 1000° C.The process steps can be repeated until the surface features are filledwith the high quality silicon oxide film.

In a further embodiment of the method described herein, the film isdeposited using a flowable CVD process. In this embodiment, the methodcomprises:

placing one or more substrates comprising a surface feature into areactor which is heated to a temperature ranging from −20° C. to about400° C. and maintained at a pressure of 100 Torr or less;

introducing at least one precursor comprising a bisaminoalkoxysilanecompound having Formula I:R¹Si(NR²R³)(NR⁴R⁵)OR⁶  Iwhere R¹ is selected from a hydrogen atom, a C₁ to C₁₀ linear alkylgroup, a C₃ to C₁₀ branched alkyl group, a C₃ to C₁₀ cyclic alkyl group,a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynyl group, a C₄ to C₁₀aromatic hydrocarbon group; R², R³, R⁴, and R⁵ are each independentlyselected from a hydrogen atom, a C₄ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; R⁶ is selected from aC₁ to C₁₀ linear alkyl group, a C₃ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₂ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; and optionallywherein R² and R³, R⁴ and R⁵, or both in Formula I can be linkedtogether to form a ring; and optionally wherein R² and R⁴ in Formula Ican be linked together to form a diamino group;

providing an oxygen source into the reactor to react with the at leastone compound to form a film and cover at least a portion of the surfacefeature;

annealing the film at one or more temperatures ranging from about 100°C. to about 1000° C. to allow the silicon-containing film to coat atleast a portion of the surface feature. The oxygen source of thisembodiment is selected from the group consisting of water vapors, waterplasma, ozone, oxygen, oxygen plasma, oxygen/helium plasma, oxygen/argonplasma, nitrogen oxides plasma, carbon dioxide plasma, hydrogenperoxide, organic peroxides, and mixtures thereof. The process can berepeated until the surface features are filled with thesilicon-containing film. When water vapors are employed as oxygen sourcein this embodiment, the substrate temperatures are preferably between−20 and 100° C., most preferably between −10 and 80° C.

In one particular embodiment, the method for depositing a film selectedfrom a silicon oxynitride and a carbon-doped silicon oxynitride in aflowable chemical vapor deposition process which comprises:

placing a substrate having a surface feature into a reactor which aremaintained at a temperature ranging from −20° C. to about 400° C.;

introducing into the reactor at least one precursor comprising abisaminoalkoxysilane compound having Formula I:R¹Si(NR²R³)(NR⁴R⁵)OR⁶  Iwhere R¹ is selected from a hydrogen atom, a C₁ to C₁₀ linear alkylgroup, a C₃ to C₁₀ branched alkyl group, a C₃ to C₁₀ cyclic alkyl group,a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynyl group, a C₄ to C₁₀aromatic hydrocarbon group; R², R³, R⁴, and R⁵ are each independentlyselected from a hydrogen atom, a C₄ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; R⁶ is selected from aC₁ to C₁₀ linear alkyl group, a C₃ to C₁₀ branched alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₂ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aromatic hydrocarbon group; and optionallywherein R² and R³, R⁴ and R⁵, or both in Formula I can be linkedtogether to form a ring; and optionally wherein R² and R⁴ in Formula Ican be linked together to form a diamino group and a nitrogen sourcewherein the at least one compound reacts with the nitrogen source toform a nitride containing film on at least a portion of the surfacefeature; and

treating the substrate with a nitrogen source to form silicon oxynitrideor a carbon-doped silicon oxynitride films to cover at least a portionof the surface feature. Optionally, the film may be exposed to UVirradiation at temperatures ranging from about 100° C. to about 1000° C.to densify the resulting films.

In a further embodiment, described herein is a process is depositsilicon-containing films employing cyclic chemical vapor deposition(CCVD) or atomic layer deposition (ALD) techniques such as, but notlimited to, plasma enhanced ALD (PEALD) or plasma enhanced CCVD (PECCVD)process. In these embodiments, the deposition temperature may berelatively high, or from about 500 to 800° C., to control thespecifications of film properties required in certain semiconductorapplications. In one particular embodiment, the process comprises thefollowing steps: contacting vapors generated from a bisaminoalkoxysilanehaving Formula I or A with a heated substrate to chemically sorb theprecursors on the heated substrate; purging away any unsorbedprecursors; introducing a reducing agent to reduce the sorbedprecursors; and purging away any unreacted reducing agent.

In another embodiment, a vessel for depositing a silicon-containing filmcomprising one or more bisaminoalkoxysilane precursor compounds havingFormula I described herein. In one particular embodiment, the vesselcomprises at least one pressurizable vessel (preferably of stainlesssteel) fitted with the proper valves and fittings to allow the deliveryof one or more precursors to the reactor for a CVD or an ALD process. Inthis or other embodiments, the bisaminoalkoxysilane precursor isprovided in a pressurizable vessel comprised of stainless steel and thepurity of the precursor is 98% by weight or greater or 99.5% or greaterwhich is suitable for the majority of semiconductor applications. Incertain embodiments, such vessels can also have means for mixing theprecursors with one or more additional precursor if desired. In these orother embodiments, the contents of the vessel(s) can be premixed with anadditional precursor. Alternatively, the bisaminoalkoxysilane precursorand/or other precursor can be maintained in separate vessels or in asingle vessel having separation means for maintaining thebisaminoalkoxysilane precursor and other precursor separate duringstorage.

In one embodiment of the method described herein, a cyclic depositionprocess such as CCVD, ALD, or PEALD may be employed, wherein at leastone bisaminoalkoxysilane precursor having Formula I and optionally anitrogen-containing source such as, for example, ammonia, hydrazine,monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen,ammonia plasma, nitrogen plasma, a plasma comprising nitrogen andhydrogen are employed.

Throughout the description, the term “ALD or ALD-like” refers to aprocess including, but not limited to, the following processes: a) eachreactant including bisaminoalkoxysilane precursor and reactive gas isintroduced sequentially into a reactor such as a single wafer ALDreactor, semi-batch ALD reactor, or batch furnace ALD reactor; b) eachreactant including bisaminoalkoxysilane precursor and reactive gas isexposed to a substrate by moving or rotating the substrate to differentsections of the reactor and each section is separated by inert gascurtain, i.e. spatial ALD reactor or roll to roll ALD reactor.

In certain embodiments, the silicon-containing films are deposited usinga flowable chemical vapor deposition (FCVD) process. In one particularembodiment of a FCVD process, bisaminoalkoxysilane precursors describedherein react with a protic reagent such as water to form a flowableliquid which can fill at least a portion of a surface feature of asubstrate and optionally treating the substrate with at least onetreatment selected from the group consisting of thermal annealing,ultraviolet (UV) light exposure, infrared (IR) to provide a solidsilicon and oxygen containing film. In another embodiment of the FCVDprocess, the bisaminoalkoxysilane precursors described herein react withan oxygen source (other than water) to form a flowable liquid which canfill at least a portion of a surface feature on a substrate andoptionally treating the substrate with at least one treatment selectedfrom the group consisting of thermal annealing, ultraviolet (UV) lightexposure, infrared (IR) to provide a solid silicon and oxygen containingfilm. In a still further embodiment of the FCVD process describedherein, the bisaminoalkoxysilane precursors described herein react witha nitrogen source to form a flowable liquid which can fill at least aportion of a surface feature on a substrate, treating the substrate withat least one treatment selected from the group consisting of thermalannealing, ultraviolet (UV) light exposure, infrared (IR) to provide asolid silicon and nitrogen containing film, and optionally convertingthe solid silicon and nitrogen containing film into a solid silicon andoxide containing by treating with an oxygen source. Thenitrogen-containing source can be selected from the group consisting ofammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, a plasmacomprising nitrogen and hydrogen, ammonia plasma, nitrogen plasma,organic amines including, but not limited to, methylamine,dimethylamine, trimethylamine, ethylamine, diethylamine, trimethylamine,tert-butylamine, ethylenediamine, ethanolamine, organic amine plasma. Inyet another embodiment of a FCVD process, the bisaminoalkoxysilaneprecursors described herein react with a plasma source to form aflowable liquid which can fill at least a portion of a surface featureof a substrate and optionally treating the substrate with at least onetreatment selected from the group consisting of thermal annealing,ultraviolet (UV) light exposure, infrared (IR) to provide a solidsilicon containing film. The plasma source can be selected from thegroup consisting of helium plasm, argon plasma, a plasma comprisinghelium and hydrogen, a plasma comprising argon and hydrogen. When aplasma is applied for FCVD or other deposition processes, the plasma canbe generated in situ or remotely. With regard to embodiments using aFCVD deposition process, in one particular embodiment, a remote plasmagenerator is used as it causes less damage to the structures on thesubstrate.

As mentioned previously, the method described herein may be used todeposit a silicon-containing film on at least a portion of a substrate.Examples of suitable substrates include but are not limited to, silicon,SiO₂, Si₃N₄, OSG, FSG, silicon carbide, hydrogenated silicon carbide,silicon nitride, hydrogenated silicon nitride, silicon carbonitride,hydrogenated silicon carbonitride, boronitride, antireflective coatings,photoresists, organic polymers, porous organic and inorganic materials,metals such as copper and aluminum, and diffusion barrier layers such asbut not limited to TiN, Ti(C) N, TaN, Ta(C) N, Ta, W, or WN. The filmsare compatible with a variety of subsequent processing steps such as,for example, chemical mechanical planarization (CMP) and anisotropicetching processes.

The deposited films have applications, which include, but are notlimited to, computer chips, optical devices, magnetic informationstorages, coatings on a supporting material or substrate,microelectromechanical systems (MEMS), nanoelectromechanical systems,thin film transistor (TFT), and liquid crystal displays (LCD).

WORKING EXAMPLES Example 1: Synthesis of bis (tert-butylamino)ethoxymethylsilane

To a solution of 72.0 g (481.7 mmol) of methyltrichlorosilane in 1.5 Lof anhydrous THF chilled to −30° C. was added 140.9 g (1926.7 mmol) oftert-butylamine drop-wise via an addition funnel while maintaining theinternal temperature of the reaction at −30° C. The resulting whiteslurry was stirred with a mechanical stirrer. Tert-butylaminehydrochloride salt was filtered off from the resulting thick slurry,washed with an additional 200 mL of hexanes, and pressed to extractresidual product possibly trapped in the salt. In a separate reaction,to a solution of 22.2 g (480.8 mmol) ethanol in 300 mL of anhydrous THFat −30° C. was added 205.0 mL (512.5 mmol) of a solution of 2.5Mn-butyllithium in hexanes drop-wise while maintaining the internaltemperature at −30° C. After addition of the nBuLi was complete, thereaction mixture turned from clear to a bright yellow suspension. Thereaction mixture was then allowed to warm to room temperature andstirred with a magnetic stir bar. After stirring overnight, the lithiumethoxide reaction mixture turned from a bright yellow suspension to awhite slurry. The lithium ethoxide reaction was then added in situ viaan addition funnel to the filtered reaction mixture from step 1 whilemaintaining the reaction at <0° C. The addition of the lithium ethoxidewas done rather quickly as the reaction was witnessed to not be thatexothermic. The resulting white suspension was warmed to roomtemperature and stirred. After the course of a few hours, the reactionmixture turned from a white suspension, to yellow, to orange. The crudereaction mixture was filtered through a medium frit isolating 25.0 g ofa brown solid reminiscent of lithium chloride. The filtrate was an amberorange solution and subjected to rotovap at 100 Torr with an oil bathtemperature of 50° C. to remove solvent. Isolated 109.26 g of crudematerial and purification was done by fractional distillation at 82° C.and 10 Torr. 51.4 g of a clear liquid was isolated at 92.5% assay.Thermogravimetric analysis (TGA)/differential scanning calorimetry (DCS)indicates a boiling point at 205° C. and 2.52% residual. Stabilitytesting showed an average purity increase of 0.38% after heating for 4days at 80° C. The assay increased from 90.18% to 90.56%.

Example 2: Synthesis of bis(tert-butylamino)methoxymethylsilane

To a solution of 72.0 g (481.7 mmol) of methyltrichlorosilane in 1.5 Lof anhydrous THF chilled to −30° C. was added 140.9 g (1926.7 mmol) oftert-butylamine drop-wise via addition funnel while maintaining theinternal temperature of the reaction at −30° C. The resulting whiteslurry was stirred with a mechanical stirrer. Tert-butylaminehydrochloride salt was filtered off from the resulting thick slurry,washed with an additional 200 mL of hexanes, and pressed to extractresidual product possibly trapped in the salt. In a separate reaction,to a solution of 15.4 g (481.7 mmol) methanol in 300 mL of anhydrous THFat −30° C. was added 202.3 mL (505.8 mmol) of a solution of 2.5Mn-butyllithium in hexanes drop-wise while maintaining the internaltemperature at −30° C. After addition of the nBuLi was complete, thereaction mixture was allowed to warm to room temperature and stirredwith a magnetic stir bar. After stirring overnight, the lithiummethoxide reaction mixture was added in situ via an addition funnel tothe filtered reaction mixture from step 1 while maintaining the reactionat <0° C. The resulting white suspension was warmed to room temperatureand stirred. A total of 250 mL of THF was added to provide adequatesolubility for the reaction to go to completion. Filtration yielded aslightly yellow powder weighting 21.5 g reminiscent of lithium chloride.Solvent was removed from the filtrate by rotovap to isolate 122.45 g ofcrude material. Purification was carried out by vacuum distillationusing a packed column at 75° C. and 10 Torr. A clear liquid was isolatedin the amount of 78.7 g. Samples were submitted for stability andTGA/DSC. DSC indicates a boiling point of 186.6° C. Further observationsshowed an average increase in assay of 0.08% (90.79% to 90.87%) afterheating in triplicate for three days at 80° C.

Example 3: Synthesis of bis(tert-butylamino)isopropoxymethylsilane

To a solution of 3.35 g (22.44 mmol) of methyltrichlorosilane in 50 mLof hexanes chilled to −30° C. was added 6.56 g (89.75 mmol)tert-butylamine drop-wise while maintaining the internal temperature ofthe reaction at −30° C. The resulting white slurry was stirred with amagnetic stir bar. Tert-butylamine hydrochloride, as a white salt, wasfiltered off from the resulting thick slurry, washed with an additional20 mL of hexanes, and pressed to extract residual product possiblytrapped in the salt. In a separate reaction, to a solution of 1.35 g(22.44 mmol) isopropyl alcohol in 30 mL of anhydrous THF at −30° C. wasadded 9.0 mL (22.4 mmol) of a solution of 2.5M n-butyllithium in hexanesdrop-wise while maintaining the internal temperature at −30° C. Afteraddition of the nBuLi was complete, the reaction mixture was thenallowed to warm to room temperature and added in situ to the filteredreaction mixture from step 1. The resulting white suspension was stirredover night after which it was filtered through a medium frit isolating awhite solid reminiscent of LiCl. The filtrate was an orange-yellowsolution. Distillation was done at 240 Torr at 50° C. to remove solvent.Upon solvent removal, more LiCl salt precipitated out and was isolatedin the amount of 0.24 g. A bulb to bulb vacuum transfer was carried outat <1 Torr and 90° C. to isolate 2.67 g a clear liquid. GC/GC-MS was runof the purified material. TGA/DCS indicates a boiling point at 212.5° C.and 0.70% residual. Stability testing conducted by heating to 80° C. for3 days showed an average purity decreased from 90.17% to 90.12%.

Example 4: Synthesis of bis(isopropylamino)tert-butoxymethylsilane

To 1.0 g (4.6 mmol) of tris(isopropylamino)methylsilane in 20 mL ofhexanes was added 0.34 g (4.6 mmol) of anhydrous tert-butanol. Over thecourse of a month, gas chromatography mass spectrometry (GC-MS)indicates evidence of desired product with a parent peak of 233 amu. Thestability of the compound was not determined.

Comparative Example 1: Synthesis ofbis(isopropylamino)ethoxymethylsilane

To 1.0 g (4.6 mmol) of tris(isopropylamino)methylsilane in 20 mL ofhexanes was added 0.21 g (4.6 mmol) of anhydrous ethanol. GC-MSindicates desired product with a parent peak of 204 amu. GC-MS and gaschromatography (GC) were run for the reaction mixture after a few daysand showed two new peaks had evolved since the last analysis. GC/GC-MSindicates the mixture exists as (in order of increasing retention time)2 parts of a mystery peak with a parent peak of 148 amu, 4 parts MTES, 1part isopropylamino-bis-ethoxymethylsilane with a parent peak of 191amu, 2 parts desired product, and 10 partstris(isopropylamino)methylsilane. This indicates ligand exchange isoccurring and that the compound is not stable. By comparison, thecompounds in Examples 1-3 having tert-butylamino groups are more stableand would be better precursors.

Comparative Example 2: Synthesis ofbis(isopropylamino)isopropoxymethylsilane Comparative Example

To 145.67 g (670 mmol) of tris(isopropylamino)methylsilane in 1.0 L ofhexanes at −20° C. was added 40.27 g (670 mmol) anhydrous isopropylalcohol. After the course of a month, GC/GC-MS indicates a ratio of 13to 6 to 43 to 31 tris-isopropoxy to bis-isopropoxy to one isopropoxysubstituted to tris(isopropylamino)methylsilane. Like ComparativeExample 1, this indicates ligand exchange is occurring and that thecompound is not stable.

Example 5: Hydrolysis of bis(tert-butylamino)ethoxymethylsilane inPresence of Iso-Propyl Alcohol

The compound bis(tert-butylamino)ethoxymethylsilane was made as shown inExample 1. One part by volume of bis(tert-butylamino)ethoxymethylsilanewas mixed with 10 parts of a solution of 20% water in isopropyl alcohol.The mixture was monitored by GC at one hour after initially mixing andshowed complete hydrolysis/condensation ofbis-tert-butylaminoethoxymethylsilane had occurred, however, nogelation. The mixture eventually gelled within 16 hours which indicatesthat the compound would be suitable in a FCVD process due to its rate ofhydrolysis/condensation then gelation. Gelation indicates thatsufficient cross-linking has occurred to turn the free-flowing liquidinto a solid which is an important characteristic for a FCVD precursor.

Example 6: Comparison Between Bis(tert-butylamino)ethoxymethylsilaneSpin-Coated Films and Tris-Isopropylaminomethylsilane Films after Aging

The compound bis(tert-butylamino)ethoxymethylsilane was made as shown inExample 1. One part by volume of bis(tert-butylamino)ethoxymethylsilanewas mixed with four parts of a solution of 20% water in isopropylalcohol and aged under ambient conditions for two hours before beingspun on a silicon wafer using a Laurell WS-400 spin coater at 2000 rpm.The wafer was thermally treated at 150° C. for 10 minutes and analyzedby Fourier Transform Infrared Spectroscopy (FTIR). The film show nodeposited Si—OH bonds similar to that of tris-isopropylaminomethylsilanefilms. Comparative tris-isopropylaminomethylsilane film was made asfollows: one part by volume of tris-isopropylaminomethylsilane was mixedwith 5 parts of a solution of 20% water in isopropyl alcohol. Themixture was aged for one hour under ambient conditions before being spunon a silicon wafer using a Laurell WS-400 spin coater at 2000 rpm. Thetris-isopropylaminomethylsilane film was aged for a shorter amount oftime then the bis(tert-butylamino)ethoxymethylsilane film due to itsfaster rate of hydrolysis/condensation. Wafer was thermally treated at150° C. for 10 minutes and analyzed by FTIR and showed no depositedSi—OH being indicative that the film is fully cross-linked. The purposeof the comparison was to show that neither films had Si—OH bonds.

Example 7: Hydrolysis of bis(tert-butylamino)ethoxymethylsilane inPresence of Iso-Propyl Alcohol and Surfynol® 61(3,5-dimethyl-1-Hexyn-3-ol) Surfactant

The compound bis(tert-butylamino)ethoxymethylsilane was made as shown inExample 1. One part by volume of bis(tert-butylamino)ethoxymethylsilanewas mixed with four parts of a solution of 20% water in a 1:4 mixture ofSurfynol® 61 to isopropyl alcohol. The mixture was aged for two hoursunder ambient conditions before being spun on a silicon wafer using aLaurell WS-400 spin coater at 2000 rpm. Likewise, one part by volume ofbis-tert-butylaminoethoxymethylsilane was mixed with four parts of asolution of 20% water in a 1:1 mixture of Surfynol® 61 to isopropylalcohol and aged for two hours before being spun as described above inExample 6. The addition of Surfynol® 61 showed no improvement inuniformity of spun films.

Example 8: Hydrolysis of Bis(Tert-Butylamino)Ethoxymethylsilane in thePresence of Ethanol

The compound bis(tert-butylamino)ethoxymethylsilane was made as shown inExample 1. One part by volume of bis(tert-butylamino)ethoxymethylsilanewas mixed with 10 parts of a solution of 20% water in ethanol. Themixture was monitored by GC at one hour after initially mixing andshowed complete hydrolysis/condensation ofbis-tert-butylaminoethoxymethylsilane had occurred, however, nogelation. The mixture eventually gelled within 16 hours which indicatesthat the compound would be suitable in a FCVD process due to its rate ofhydrolysis/condensation then gelation.

Example 9: Hydrolysis of bis(tert-butylamino)ethoxymethylsilane in thePresence of Ethanol

The compound bis(tert-butylamino)ethoxymethylsilane was made as shown inExample 1. One part by volume of bis(tert-butylamino)ethoxymethylsilanewas mixed with four parts of a solution of 20% water in ethanol. Themixture was monitored by GC at one hour after initially mixing andshowed complete hydrolysis/condensation ofbis-tert-butylaminoethoxymethylsilane had occurred, however, nogelation. The mixture eventually gelled within 16 hours which indicatesthat the compound would be suitable in a FCVD process due to its rate ofhydrolysis/condensation then gelation.

Example 10: Hydrolysis of bis(tert-butylamino)ethoxymethylsilane inPresence of Ethanol

The compound bis(tert-butylamino)ethoxymethylsilane was made as shown inExample 1. One part by volume of bis-tert-butylaminoethoxymethylsilanewas mixed with four parts of a solution of 20% water in ethyl alcohol.The mixture was aged for two hours under ambient conditions before beingspun on a silicon wafer using a Laurell WS-400 spin coater at 2000 rpm.The resulting film was a white powder and non-uniform. The presentexample shows that the addition of alcohol provided different physicalcharacteristics of the spun film.

Example 11: Hydrolysis of bis(tert-butylamino)methoxymethylsilane inPresence of Iso-Propyl Alcohol

The compound bis(tert-butylamino)ethoxymethylsilane was made as shown inExample 2. One part by volume of bis-tert-butylaminomethoxymethylsilanewas mixed with 10 parts of a solution of 20% water in isopropyl alcohol.The mixture was monitored by GC at one hour after initially mixing andshowed complete hydrolysis/condensation ofbis-tert-butylaminomethoxymethylsilane had occurred, however, nogelation. The mixture eventually gelled within 16 hours which indicatesthat the compound would be suitable in a FCVD process due to its rate ofhydrolysis/condensation then gelation.

Example 12: Hydrolysis of bis(tert-butylamino)methoxymethylsilane inPresence of Iso-Propyl Alcohol

The compound bis(tert-butylamino)ethoxymethylsilane was made as shown inExample 2. One part by volume of bis-tert-butylaminomethoxymethylsilanewas mixed with four parts of a solution of 20% water in isopropylalcohol. The mixture was monitored by GC to determine the extent ofhydrolysis/condensation of the precursor at 5 minutes, 30 minutes, and 2hours after initially mixing and showed evidence that a significantamount of bis-tert-butylaminomethoxymethylsilane had undergonehydrolysis/condensation, however, no gelation occurred. The mixtureeventually gelled within 16 hours which indicates that the compoundwould be suitable in a FCVD process due to its rate ofhydrolysis/condensation then gelation.

Example 13: Deposition of Flowable Carbon-Doped Silicon Oxynitride FilmUsing bis(tert-butylamino)methoxymethylsilane

The flowable CVD films were deposited onto medium resistivity (8-12 Ωcm)single crystal silicon wafer substrates and silicon pattern wafers. Incertain examples, the substrate may be exposed to a pre-depositiontreatment such as, but not limited to, a plasma treatment, thermaltreatment, chemical treatment, ultraviolet light exposure, electron beamexposure, and/or other treatments to affect one or more properties ofthe films.

The depositions were performed on an Applied Materials Precision 5000system in a modified 200 mm DXZ chamber, using either a silane or a TEOSprocess kit. The PECVD chamber was equipped with direct liquid injection(DLI) delivery capability. The precursors were liquids with deliverytemperatures dependent on the precursor's boiling point. To depositinitial flowable nitride films, typical liquid precursor flow rates were100-5000 mg/min, in-situ plasma power density was 0.25-3.5 W/cm²,pressure was 0.75-12 Torr. To densify the as-deposit flowable films, thefilms were thermally annealed and UV cured in vacuum using the modifiedPECVD chamber from 100˜500° C. or from 300˜400° C. Thickness andrefractive index (RI) at 632 nm were measured by a SCI reflectometer orWoollam ellipsometer. Typical film thickness ranged from 10 to 2000 nm.Bonding properties hydrogen content (Si—H, C—H and N—H) of thesilicon-based films were measured and analyzed by a Nicolet transmissionFourier transform infrared spectroscopy (FTIR) tool. All densitymeasurements were accomplished using X-ray reflectivity (XRR). X-rayPhotoelectron Spectroscopy (XPS) and Secondary ion mass spectrometry(SIMS) analysis were performed to determine the elemental composition ofthe films. The flowability and gap fill effects on patterned wafers wereobserved by a cross-sectional Scanning Electron Microscopy (SEM) using aHitachi S-4700 system at a resolution of 2.0 nm.

Flowable CVD depositions were conducted using a design of experiment(DOE) methodology. The experimental design includes: precursor flow from100 to 5000 mg/min, preferably 1000 to 2000 mg/min; NH₃ flow from 100sccm to 1000 sccm, preferably 100 to 300 sccm; pressure from 0.75 to 12Torr, preferably 6 to 10 Torr; RF power (13.56 MHz) 100 to 1000 W,preferably 100˜500 W; Low-frequency (LF) power 0 to 100 W; anddeposition temperature ranged from 0 to 550° C., preferably 0 to 40° C.The DOE experiments were used to determine what process parametersproduced the optimal film with good flowability.

In one experiment, the process conditions used to provide the mostoptimal film properties are as follows:bis(tert-butylamino)methoxymethylsilane flow=1000 mg/min, NH₃ flow=0˜450sccm, He=100 sccm, Pressure=8 torr, power=300˜600 W, andtemperature=30˜40° C. On a blanket Si wafer, wet and tacky SiCON filmswere deposited with the shrinkage ranging from 10% to 50% after thermalannealing and UV cure. Review of cross-sectional scanning electronmicroscopy (SEM) images showed that bottom-up, seamless, and void-freegap-filling was achieved on pattern wafers, or wafers having at leastone surface feature, using bis(tert-butylamino)methoxymethylsilane in aflowable CVD process.

The invention claimed is:
 1. A bisaminoalkoxysilane compound having aFormula I:R¹Si(NR²R³)(NR⁴R⁵)OR⁶  I wherein R¹ is a methyl group; R² and R⁴ areeach hydrogen atoms; R³ and R⁵ are each selected from the groupconsisting of tert-butyl and tert-pentyl; and R⁶ is selected from a C₁to C₃ linear alkyl group and a C₃ to C₅ branched alkyl group.
 2. Thebisaminoalkoxysilane compound of claim 1 wherein the compound is atleast one selected from the group consisting ofbis(tert-butylamino)methoxymethylsilane,bis(tert-butylamino)ethoxymethylsilane, andbis(tert-butylamino)isopropoxymethylsilane.
 3. A method for forming asilicon-containing film on at least one surface of a substratecomprising: providing the substrate in a reactor; and forming thesilicon-containing film on the at least one surface by a depositionprocess selected from the group consisting of atomic layer deposition(ALD), plasma enhanced ALD (PEALD), and plasma enhanced cyclic CVD(PECCVD) using at least one precursor comprising a bisaminoalkoxysilanehaving Formula I:R¹Si(NR²R³)(NR⁴R⁵)OR⁶  I where R¹ is a methyl group; R² and R⁴ are eachhydrogen atoms; R³ and R⁵ are each selected from the group consisting oftert-butyl and tert-pentyl; and R⁶ is selected from a C₁ to C₃ linearalkyl group and a C₃ to C₅ branched alkyl group.
 4. A silicon-containingfilm formed using the compound of claim
 1. 5. The silicon-containingfilm formed according to the method of claim 3.